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Patented Dec. 24, 1946
2,413,050 I
UNITED STATES PATENT OFFICE
2,413,050
ALKYL SILICON CHLORIDES AND
THEIR PREPARATION
James Franklin Hyde, Corning, N. Y., assignor
to Corning Glass Works, Corning, N. Y., a cor- _
poration of New York
No Drawing. Application April 21, 1945,
Serial No. 589,689 ,
_
I 5 Claims.
1
(Cl. 260-607)
.
temperature. Then the supernatant liquor is
carefully siphoned to a .closed dropping funnel
This invention relates to new compositions of
matter and their preparation and, more particu
larly, to organo-silicon chlorides and methods of
preparing them.
‘
' on the coupling reactor.
In coupling the alkyl Grignard reagent pre
.
The present application is a continuation-in
part of my copending applications, Serial Num
5 pared as described above with silicon tetrachlo-l
ride, it is preferable to use the latter in excess
ber 432,528 ?led February 26, 1942, and Serial
Number 490,517 ?led June 11, 1943, said applica
tions being assigned to the assignee of the present
in order to favor the monoalkyl derivative among
the various distribution products obtained. In
common with Grignard synthesis in general,
10 vigorous stirring is employed to minimize local
ized reaction. Also, the Grignard reagent is ad
invention.
'
‘
The primary object of my invention is to pro
,
vide a new series of compounds having the gen
eral formula RSiCls where R is'an alkyl radi
cal having from 10 to 31 carbon atoms. Other
objects and advantages of my invention will be 15
apparent from the following description.
The general procedure for the preparation of
mitted slowly ‘into the silicon tetrachloride which
is diluted with a solvent, such as ether. The
diluent may be any liquid which may not react
with the reagents or product but a hydrocarbon
is preferred over ether inasmuch as the by-pro
. duced magnesium chloride is partiallysoluble in -
the ether and is solvated by it, making subsequent
the compositions of my invention involves the
formation of the suitable Grignard reagent and - ?ltration more difficult. The actual coupling
the coupling of this silicon tetrachloride. In both 20 may be conducted at re?ux temperature or at
a reduced temperature, the latter being preferred.
of these operations as well as in the subsequent
To obtain a. reduced temperature, external cool
working up of the product, it is obvious from the
ing is necessary. When the addition of the Gn'yg-j
nature of the reagents and the products that an
nard reagent is completed, it is good practice
hydrous materials should be used and that the
conditions of operation be such that air and 25 to stir the mixture a few hours at reflux temper
ature to break up salt lumps which may occlude
moisture are carefully excluded if the maximum
reagent or product. The product is7 ?lteredin'
yields are to be obtained. ‘The alkyl chloride
any conventional manner that insures minimum
employed should be free of its corresponding alco- ‘
exposure to the atmosphere. The ?ltrate, includ
hol and the solvents or_diluents used should also
be free of alcohol. For preparing the Grignard 30 ing salt cake rinsings, is fractionally distilled in
reagent either relatively pure magnesium or any
one of the several magnesium alloys may be used.
Since the Grignard reagent preparation involves
a, surface reaction the magnesium metal should
vacuo to isolate the pure alkyl silicon trichlorides.
For a better understanding of my invention,
reference should be had‘to the following exam
ples which are included merely by way of illus
be in a form such as will provide a reasonably 35 tration and not limitation.
large surface, preferably in the form of turnings.
EXAMPLE 1
Stirring is required during the formation of the
Grignard reagent to provide adequate mixing
‘
Dodecyl silicon trichlorz'de
but it should not be so vigorous that the reaction
95 parts (0.43 mol) of lauryl chloride
nuclei are buffed off the magnesium particles 40 (CizHzsCl) dissolved in 68 parts (0.92 mol) of
and the reaction thereby impeded. Since this re
anhydrous ethyl ether were added slowly to 12.5
parts (0.51 mol) of magnesium turningsunder
action is often ditlicult to start, it is advisable
to preheat the magnesium turnings in' a bit of
35 parts of ethyl ether. The latter was in a
iodine vapor or to initiate the reaction with a
3-necked glass ?ask provided with a stirrer, a
little ethyl bromide in ether. Once the reaction 45 condenser, and a dropping funnel, respectively.
The addition of the chloride was accomplished
is initiated the heat of reaction will carry the
reaction on at the reflux temperature of the
through the dropping funnel. Reaction was ini
The alkyl chloride
should be admitted , tiated by the addition of a little bromide in ether.
ether.
‘
at such a rate (relatively slow) that a gentle re
The addition of the chloride was such thereafter
?ux is maintained. After all of the alkyl chlo
as to maintain a gentle re?ux of the ether. After
ride has been admitted, it is good practice to stir
all the chloride had been admitted, the reaction
for an additional hour or two while holding at
mass was stirred for another hour with the tem
re?ux. temperature. Finally, the agitation is
perature being held at re?ux. The stirring was
then stopped and the mixture allowed to stand
stopped and the mixture allowed to stand for
some time to permit settling and cooling to room 55 to permit settling of the salt and coolingto room
' ~
9,418,050
4
I
temperature. The supernatant liquor was then
fraction boiling at 159 to 182° C. at 13 mm was
carefully siphoned into a closed dropping funnel _
identi?ed by analysis to be CuHuSiCl. Its
on the coupling reactor which, likewise, was a
density was 0.95 g./cc. at 22° C.
3-necked flask provided with the aforementioned
In general, the monoalkylsilicon trichlorides are
useful for rendering normally non-water repel
funnel, a stirrer, and a condenser.
The Grignard reagent so produced was added
to a twofold excess of 140 parts of silicon tetra
chloride (0.83 mol) in 150 parts of benzene. The
reaction mass was stirred for 3 hours and then
.
lent surfaces water repellent. They are par
ticularly emcacious in the waterproo?ng of glass
and ceramic materials, but may also be used in
the treatment of cellulose fabrics such as cotton.
heated to re?ux temperature for another 3 hours 10 I have found that the series of compounds of the
with stirring being continued. The product was
?ltered and the ?ltrate was then fractionally dis
tilled, yielding a fraction at 162-171“ C. at 18
present invention, namely, those having the gen
eral formula RSlCl: where R is an alkyl radical
having from 10 to 31 carbon atoms are outstand
ing in their waterproo?ng effectiveness.
mm. in an amount corresponding to 67% » of
theory.
lows:
An analysis of this fraction was as fol
15
The latter property in combination with that of
Per cent 0 Per cent B- Percent Cl Per cent ‘Bi
F0
I have also discovered that this series of com
pounds possess the additional property of being
extremely effective lubricating agents for glass.
d ......... ..
41.7
8.52
34.2
9.02
Th‘alry ........ .-
41.4
8.23
36.2
9.22
waterproo?ng adapts them for use in the pro
20 duction of glass yarn from glass ?bers. As glass
?bers are formed they possess great strength
which, however, decreases‘ rapidly upon exposure
to moisture. Accordingly it is desirable to pro
EXAMPLE 2
Tetradeclllsilico? trichloride
Tetradecylsilicon trichloride (CuHneSiCls) was
prepared in a manner similar to the preparation
of the dodecylsilicon 'trichloride' of Example 1
tect' their surfaces as soon as possible from the
25 effects of moisture. From 100 to 400 ?bers are
bound together to form strands which are wound
on packages in such a manner that the strands
can be unwound and processed thereafter in the
with the exception that the Grignard reagent
conventionaltextile machines. To facilitate the
which was prepared from myristyl bromide 30 binding of the ?bres into strands a “binding
(CuI-IzeBr) was diluted with ether to a‘ relatively
fluid" is employed which serves to stick the ?bers
low concentration prior to coupling with silicon
tetrachloride. The crude coupling product was
directly distilled and a fraction collected in the
together while at the same time lubricating them
against themselves and against abrasion from
fabricating equipment. The compounds of my
invention not only serve to “waterproof" the
glass ?bers but also to bind and to lubricate to
the proper degree the ?bers during their forma
tion into strands.
range of 131-132" C. at 0.8 mm. This fraction
was identi?ed by analysis as CnHzsSiCls. The
yield was 50% of the theoretical.
EXAMPLE 3
'
Octadecylsil?i‘on trichloride
Octadecylsilicon trichlorlde was likewise pre
pared in a manner similar to that described in
Example 1.
The Grignard reagent was made
from pure stearyl bromide (Cl8H3'lSlB1‘).__ An
ether solution containing 3.54 mols of the Gri
gnard reagent was slowly introduced into a cou
pling reactor containing 7.3 mols of silicon tetra
chloride and 1.5 liters of benzene. The coupling
product was ?ltered in the usual manner and
the ?ltrate fractionally distilled in vacuo. A
40
I claim:
1. A composition of matter having the general
.formula RSlCl: wherein R is an alkyl radical
- having from 10 to 31 carbon atoms.
I 2. A composition of matter having the general
formula RSiCls wherein R is an alkyl radical
having from 12 to 18 carbon atoms.
3. Octadecylsilicon trichloride.
_4. Dodecylsilicon trichloride.
5. Tetradecylsilicon trichloride.
JAMES FRANKLIN HYDE.